Tie-layer materials for use with ionomer-based films and sheets as skins on other materials

ABSTRACT

The present invention relates to new tie-layer materials for making (1) new multilayer structures formed from one or more ionomers and one or more new tie-layers including a (co) extrudable tie resin (CTR), and optionally a backing layer to form laminates, (2) new composite articles made from these laminates in combination with optional substrate materials, and (3) new methods of making composite articles from these laminates by shaping and subsequently contacting them with a substrate material.

CROSS REFERENCE TO RELATED APPLICATIONS

[0001] This application claims the benefit of Provisional ApplicationNo. 60/473,783 filed May 27, 2003, the disclosure of which isincorporated by reference.

FIELD OF THE INVENTION

[0002] The present invention relates to new tie-layer materials formaking (1) new multilayer structures formed from one or more ionomersand one or more new tie-layers including a (co)extrudable tie resin(CTR), and optionally a backing layer to form laminates, (2) newcomposite articles made from these laminates in combination withoptional substrate materials, and (3) new methods of making compositearticles from these laminates by shaping and subsequently contactingthem with a substrate material.

BACKGROUND OF THE INVENTION

[0003] Durable, glossy fascia associated with articles such asautomobiles, luggage, appliances, and other durable articles made fromplastics increase both the aesthetic appeal and the utility of thesearticles. These article attributes are provided, in part, through theincorporation of ionomer materials.

[0004] Ionomer materials are known in the art, and are useful inlaminates to coat various substrates to form composite articles. See,for example, U.S. Pat. Nos. 3,264,272, 5,482,766, 4,148,972, 5,543,233,4,800,130, 4,656,098, 5,206,294, 4,335,175, U.S. patent applicationPublication Nos. 2001/003021, 2002/0114951, 2002/0114965, DE 36 26 809A, EP 0 721 856, EP 0 342 897, EP 1 279 493, EP 0 287 839, JP 08269409,JP 2000085062, JP 04052136, WO 01/78981, WO 02/078953, and WO 02/078954.Ionomer laminates are useful for their scratch and abrasion resistance,as well as toughness and aesthetic appeal. However, with a growingdemand for new applications for ionomer laminates and composite articlesproduced from ionomer laminates, there continues to be a need for newmaterials to produce new laminates for the wide array of applications.

[0005] The invention fulfills this need by providing for new tie-layermaterials that may be used in new ionomer laminates and new compositearticles produced from those ionomer laminates

SUMMARY OF THE INVENTION

[0006] In an embodiment, the invention relates to a laminate comprisingan ionomer layer and a tie-layer comprising a (co)extrudable tie resin(CTR).

[0007] In another embodiment, the invention relates to a compositecomprising an ionomer layer, a tie-layer comprising a CTR, and asubstrate, optionally including a backing layer.

[0008] In one embodiment, the invention relates to a laminate comprisingan ionomer layer, a tie-layer comprising a CTR, and a backing layer;wherein the tie-layer is disposed between the ionomer layer and thebacking layer.

[0009] In another embodiment, the invention relates to a compositecomprising an ionomer layer, a tie-layer comprising a CTR, and asubstrate; wherein the tie-layer is disposed between the ionomer layerand the substrate.

[0010] In another embodiment, the invention relates to a compositecomprising a tie-layer having a first side and a second side, whereinthe first side is contacted to an ionomer layer, and the second side issecured to a substrate comprising at least one thermoplastic; andwherein the tie-layer comprises a CTR.

[0011] In yet another embodiment, the invention relates to a compositearticle comprising:

[0012] a) an ionomer layer;

[0013] b) a tie-layer;

[0014] c) a backing layer; and

[0015] d) a substrate;

[0016] wherein the ionomer layer and tie-layer contact one another andwherein the tie-layer comprises a CTR.

[0017] Additionally, the invention also provides for a method of forminga composite article comprising:

[0018] (a) providing a laminate;

[0019] (b) forming the laminate into a shape, the laminate comprising anionomer layer contacted to a tie-layer comprising a CTR; and

[0020] (c) securing a substrate to the tie-layer of the laminate to formthe composite article.

[0021] In another embodiment, the invention provides for a method offorming a composite article comprising:

[0022] (a) coextruding at least two materials to form a laminate;

[0023] (b) thermoforming the laminate into a shape, the laminatecomprising an ionomer layer contacted to a tie-layer comprising a CTR;and

[0024] (c) injection molding a substrate layer against the tie-layer ofthe laminate to form the composite article.

[0025] The invention also provides for a composite article formed by themethod comprising:

[0026] (a) forming a laminate comprising an ionomer layer and atie-layer comprising a CTR;

[0027] (b) coextruding the ionomer layer and the tie-layer with abacking layer;

[0028] (c) forming a shape from the laminate, resulting in a shapedlaminate; and

[0029] (d) securing a substrate material to the shaped laminate suchthat the substrate material is secured to the backing layer.

[0030] In any of the previous embodiments, a CTR may be selected fromthe group consisting of an amine containing polymer, an epoxy containingpolymer, a polar copolymer, a polymer made from carbon monoxide, apolymer made from a diacid, a polymer made from an anhydride, and apolyolefin grafted with acrylic acid.

[0031] In any of the previous embodiments, the ionomer layer may includea first ionomer layer and a second ionomer layer.

[0032] In the previous embodiments, the first ionomer layer or thesecond ionomer layer may be pigmented, natural, or clear.

[0033] Additionally, in any of the previous embodiments, the inventionprovides for an optional backing layer.

DETAILED DESCRIPTION OF THE INVENTION

[0034] As used herein, the term “layer” refers to each of the one ormore materials, the same or different, in an essentially planar form,that are secured to one another by any appropriate means such as by aninherent tendency of the materials to adhere to one another, or byinducing the materials to adhere as by a heating, radiative, chemical,or some other appropriate process to form laminates.

[0035] As used herein, the term “laminate” refers to any number of thesame or different materials in layer form, each layer being secured toone another by any appropriate means such as by an inherent tendency ofthe materials to adhere to one another in a coextrusion process, or byinducing the materials to adhere as by a heating, radiative, chemical,or some other appropriate process. Some non-limiting process examples offorming laminates are coextrusion, thermal lamination, or adhesivebonding, or some combination thereof. Suitable adhesives include acrylicadhesives (both solvent and water-based), flexible epoxy adhesives, andhot melt adhesives. In an embodiment, the adhesive is not based onpolyurethane (a non-polyurethane adhesive). The laminate may include anoptional backing layer.

[0036] As used herein, the term “shaped laminate” refers to a laminatein either a planar or three dimensional form that is suitable forproduction of a finished article.

[0037] As used herein, the term “tie-layer” refers to a layer bonded tothe ionomer layer(s). In most embodiments that include a backing layer,the backing layer is bonded to the ionomer layer(s) with the tie-layer.In embodiments that include a substrate, the substrate is bonded to theionomer layer(s) with the tie-layer. Each tie-layer may comprisemultiple layers.

[0038] As used herein “(co)extrudable tie resins” refers to polymers ormodified polymers, as further defined below, suitable for makingtie-layers by either extrusion or coextrusion. CTRs are thermoplasticmaterials that are solid at room temperature and soften or melt withincreasing temperature, becoming formable.

[0039] As used herein, “(meth)acrylate” refers to either methacrylate oracrylate esters and “(meth)acrylic acid” refers to either methacrylicacid or acrylic acid.

[0040] As used herein, “polar copolymer” implies a copolymer of one ormore C₂-C₁₀ α-olefins copolymerized with one or more polar monomersselected from the group consisting of ethylenically copolymerizableC₃-C₂₃ monoacid monomers; C₄-C₃₃ esters of ethylenically copolymerizablemonoacid monomers; and C₃-C₂₃ vinyl esters.

[0041] As used herein, “hydrocarbon” refers to molecules or segments ofmolecules containing primarily hydrogen and carbon atoms. “Hydrocarbon”also includes halogenated versions and versions containing herteroatoms.

[0042] As used herein, “backing layer” refers to a tie-layer that formsthe surface opposite from the ionomer surface of the multilayeredlaminate. In most embodiments, the backing layer requires a tie-layer ofa different composition to bond it to the ionomer layer(s).

[0043] As used herein, “composite article” refers to an article formedfrom a multilayer laminate secured to a substrate.

[0044] As used herein, “substrate” refers to that part of the compositearticle that is behind the multilayered laminate, and typically providesthe largest proportion of the mass of the composite article. Ittherefore governs the range of many of the physical properties of thecomposite article such as stiffness, tensile strength, impact strength,etc. Surface properties of the composite article, such as gloss, scratchresistance, abrasion resistance, color, appearance, “flop”, are usuallyunaffected by the substrate.

[0045] As is well known in the art, the demarcation between “film” and“sheet” is nominally 250 μm. However, as used herein the term “sheet”can refer to single layered or multilayered structures with thicknessesthat are greater than, equal to or less than 250 μm.

[0046] As used herein, the term “Groups” or “Group” refers to the newnumbering scheme for the Periodic Table Groups as in HAWLEY'S CONDENSEDCHEMICAL DICTIONARY 852 (13th ed. 1997).

[0047] In an embodiment, the composite article provides for amultilayered sheet secured to a substrate. The multilayered sheetprovides for an ionomer layer (surface layer), pigmented or naturalcolor, and a tie-layer, pigmented or natural color. The multilayeredsheet is secured to a substrate.

[0048] In another embodiment, the composite article provides for amultilayered sheet including a backing layer. The multilayered sheetprovides for an ionomer layer (surface layer), pigmented or naturalcolor, a tie-layer, pigmented or natural color, and a backing layer.

[0049] In another embodiment, the composite article provides for amultilayered sheet secured to a substrate. The multilayered sheetprovides for a set of ionomer layers comprising a surface layer of clearionomer and a sub-surface layer of pigmented or clear ionomer, and apigmented or natural color tie-layer. The multilayered sheet is securedto a substrate.

[0050] The composite article also provides for a multilayered sheetincluding a backing layer. The multilayered sheet provides for a set ofionomer layers comprising a surface layer of clear ionomer and asub-surface layer of pigmented or clear ionomer, a pigmented or naturalcolor tie-layer, and a pigmented or natural color backing layer.

[0051] In yet another embodiment, the composite article provides for amultilayered sheet including a backing layer secured to a substrate. Themultilayered sheet provides for an ionomer layer (surface layer),pigmented or natural color, a tie-layer, pigmented or natural color, anda pigmented or natural color backing layer. The multilayered sheet issecured to a substrate.

[0052] In an embodiment, the composite article provides for amultilayered sheet including a backing layer secured to a substrate. Themultilayered sheet provides for a set of ionomer layers comprising asurface layer of clear ionomer and a sub-surface layer of pigmented orclear ionomer, a pigmented or natural color tie-layer, and a pigmentedor natural color backing layer. The multilayered sheet is secured to asubstrate.

[0053] In the embodiments described above, all of the aforementionedlayers, with the exception of the surface layer, may also be multiplelayers, i.e, sets of ionomer layers, sets of tie-layers and/or sets ofbacking layers. These embodiments may also include sets of substratelayers.

[0054] In the embodiments described above, the tie-layer may comprise ablend of a maleated polypropylene and an acid polymer, more preferablyan acid terpolymer.

[0055] In any of the structures described above, the tie-layerpreferably comprises an epoxy containing polymer such as ethyleneglycidyl methacrylate copolymers and terpolymers wherein the additionalmonomer is selected from the group consisting of methyl(meth)acrylate,ethyl(meth)acrylate, propyl(meth)acrylate, and butyl(meth)acrylate.

[0056] In any of the structures described above, the tie-layerpreferably comprises ethylene(meth)acrylic acid copolymers alone or inblends with polyolefins and/or acid terpolymers.

[0057] In any of the structures described above, the tie-layerpreferably comprises ethylene alkyl(meth)acrylate ester copolymers, morepreferably wherein the alkyl(meth)acrylate monomer is selected from thegroup consisting of methyl(meth)acrylate, ethyl(meth)acrylate,propyl(meth)acrylate, butyl (meth)acrylate, and blends thereof. Theethylene alkyl(meth)acrylate ester copolymer may be used alone or inblends with polyolefins and/or acid copolymers or terpolymers.

[0058] Ionomer

[0059] Ionomers useful in the present invention are ionic compoundswhich are copolymers of C₂ to C₄ α-olefin derived units (ethylene isherein included as an “α-olefin”), and ethylenically copolymerizableacidic monomers including C₃ to C₆ α,β-ethylenically unsaturatedcarboxylic acids and monoesters of C₄ to C₆ unsaturated diacids, andwhich contain one or more kinds of metallic or organic cationsassociated with at least 5% of the acidic pendant groups of the polymer.Typical ionomers and methods of production are disclosed in, forexample, U.S. Pat. Nos. 3,264,272, 4,911,451, 5,210,138, and 5,929,174;and WO 98/52981, 95/11929, 96/23009, 97/11995, and 97/02317, anddescribed in COMPREHENSIVE POLYMER SCIENCE 755-772 (Colin Booth & ColinPrice, ed. Pergamon Press 1989), in particular relating toethylene-based materials.

[0060] The metal ion or ions suitable for forming the ionic copolymersof the present invention comprise mono, di or tri-valent metal ions inthe Groups 1 through 13 of the Periodic Table of Elements. Embodimentsinclude the following metal ions: Na⁺, K⁺, Li⁺, Cs⁺, Ag⁺, Hg⁺, Cu⁺,Be²⁺, Mg²⁺, Ca²⁺, Sr²⁺, Ba²⁺, Cu²⁺, Cd²⁺, Hg²⁺, Pb²⁺, Fe²⁺, Co²⁺, Ni²⁺,Zn²⁺, Al²⁺Sc³⁺, Fe³⁺, Al³⁺ and Yt³⁺. In the various ions mentionedabove, Mg²⁺, Na⁺ and Zn²⁺ are metals used in desirable embodiments.Reaction of the carboxylic acid groups of the ionomer and a metal ionderived from a desirable metal compound (metal oxide, metal chloride,etc.) is referred to as “neutralization”.

[0061] The ionomers useful in the present invention, either alone or asa blend of two or more ionomers, generally include more than 60 wt %α-olefin derived units in one embodiment by weight of the ionomer, andmore than 70 wt % α-olefin derived units in another embodiment, and morethan 80 wt % α-olefin derived units in one embodiment, and more than 85wt % α-olefin derived units in yet another embodiment, and less than 95wt % α-olefin derived units in another embodiment, and less than 85 wt %α-olefin derived units in another embodiment, and less than 75 wt %α-olefin derived units in yet another embodiment, and from 60 to 95 wt %α-olefin derived units in another embodiment, wherein a desirable rangeof α-olefin derived units that make up the ionomer is any combination ofany upper limit with any lower limit described herein; and from 5 to 25wt % of ethylenically copolymerizable acid monomers in one embodiment,and from 1 to 15 wt % of ethylenically copolymerizable acid monomers inanother embodiment, and from 8 to 20 wt % of ethylenicallycopolymerizable acid monomers in another embodiment, wherein a desirableembodiment of a useful ionomer may comprise any upper wt % limit and anylower wt % limit of any ethylenically copolymerizable acid monomersdescribed herein.

[0062] The polymer may be neutralized to form the ionomer to any degreebetween 10% to 100% based on the total amount of neutralizablecarboxylate groups in one embodiment, and from 20% to 80% in anotherembodiment, and from 40% to 75% in yet another embodiment, and from 5%to 70% in yet another embodiment, provided the necessary scratch and marresistance is maintained. A desirable level of neutralization mayinclude any upper neutralization % limit and any lower neutralization %limit described herein.

[0063] One embodiment of an ionomer can be described as in the followingstructure (1):

[0064] wherein X¹ and X² can be the same or different and are hydrogenor a C₁ to C₆ alkyl, and M^(n+) is a metal ion or NH₄ ⁺. Of course, itis understood that when n is >1, such as with a divalent metal ion suchas Zn²⁺, that charge neutrality for the ionomer is achieved by reactionwith a total of n acid groups from either the same polymer chain, or anadjacent polymer chain. The structure (1) is not intended to beconstrued that the ionomer is a block copolymer or limited to being ablock copolymer. The values of i, j, and k are determined by thefollowing relationships (2) and (3): $\begin{matrix}{\frac{j + k}{i + j + k} = Q} & (2) \\{{\frac{k}{j + k} = P}\quad} & (3)\end{matrix}$

[0065] wherein Q is from 10 to 40% of the polymer units derived from theacidic monomer(s) relative to the total weight of the ionomer in oneembodiment, and from 15 to 20% of polymer units derived from the acidicmonomer(s) in another embodiment, and P is from 10 to 80% of the acidicgroups neutralized with the metallic ions in one embodiment, and from 20to 70% of the acidic groups neutralized with the metallic ions inanother embodiment, and from 20 to 60% in yet another embodiment, andfurther ranges as stated above. The polymer component i, derived fromethylene in one embodiment, can be linear or branched.

[0066] The ionomers or blends of two or more ionomers should be capableof being formed into a sheet having a thickness of from 15 μm to 6 mm,and from 25 μm to 700 μm in another embodiment, and possess desiredproperties, i.e., a high or low gloss, scratch resistance, abrasionresistance, etc. Useful ionomers or ionomer blends have a peak melttemperature of greater than 75° C. in one embodiment, and between 75° C.and 150° C. in another embodiment, and between 75° C. and 95° C. in oneembodiment, and between 80° C. and 90° C. in another embodiment; and amelt index (MI) of between 0.1 dg/min and 30 dg/min (ASTM D1238,190/2.16) in one embodiment, from 0.2 to 8 dg/min in one embodiment,from 0.5 to 5 dg/min in another embodiment, and from 0.8 to 2.5 dg/minin yet another embodiment, wherein a desirable range may be anycombination of any upper MI limit with any lower MI limit describedherein.

[0067] The ionomers useful in the present invention should provide highscratch and impact resistance to the laminate and composite article. Theionomers or ionomer blends have a 1% secant flexural modulus (ASTMD-790) of greater than 50 MPa in one embodiment, and greater than 100MPa in another embodiment, and greater than 200 MPa in anotherembodiment, and greater than 400 MPa in yet another embodiment, between50 and 400 MPa in one embodiment, and from 100 to 350 MPa in anotherembodiment. Desirable ionomers are ethylene methacrylic acid copolymerionomers and ethylene acrylic acid copolymers ionomers and the like.Particularly desirable ionomers are those that are sodium, zinc ormagnesium salts of acrylic acid or methacrylic acid copolymers.

[0068] Further, in a desirable embodiment, certain blends of ionomersbased on ethylene acrylic acid copolymer neutralized with divalent andmonovalent metal ions (cations) such as Zn²⁺ and Na⁺, display asynergistic MI “uplift” as disclosed in, for example, U.S. Pat. Nos.5,210,138, and 5,929,174 are useful. In one embodiment of the invention,one or more of the ionomer layers that make up the laminate is a blendof a first ionomer having an MI value of from 0.6 to 1.0 dg/min, and asecond ionomer having an MI value of from 2.1 to 3.0 dg/min. The blendof the first and second ionomers includes from 45 wt % to 95 wt % of thefirst ionomer in one embodiment, and from 55 wt % to 85 wt % of thefirst ionomer in another embodiment, and from 65 wt % to 80 wt % of thefirst ionomer in yet another embodiment, and from 72 wt % to 78 wt % ofthe first ionomer in yet another embodiment, and 75 wt % of the firstionomer in yet another embodiment, wherein a desirable range may includeany upper wt % limit and any lower wt % limit described herein. Theblends may include blends of two or more ionomers having differentmetallation (different metals and/or different % of metallation),different MI values, or a combination of variables.

[0069] Other examples of ionomers useful in the present inventioninclude, but are not limited to, butadiene-acrylic acid copolymerionomers, perfluorsulfonate ionomers, perfluorocarboxylate ionomers,telechelic polybutadiene ionomers, sulfonated ethylene-propylene-dieneterpolymer ionomers, styrene-acrylic acid copolymer ionomers, sulfonatedpolystyrene ionomers, sulfonated polypentenamer ionomers, telechelicpolyisobutylene sulfonated ionomers, alkyl methacrylate-sulfonatecopolymer ionomers, styrene-based polyampholytes ionomers and acid-amineionomers and the like. Typical examples of ionomers employing salts ofcarboxylic acid type pendent groups are disclosed in GB 1,011,981; U.S.Pat. Nos. 3,264,272; 3,322,734; 3,338,734; 3,355,319; 3,522,222; and3,522,223. Typical examples of ionomers employing phosphonate-typependent groups include those disclosed in U.S. Pat. Nos. 3,094,144;2,764,563, 3,097,194; and 3,255,130. Typical examples of ionomersemploying sulfonate-type pendent groups include those disclosed in U.S.Pat. Nos. 2,714,605; 3,072,618; and 3,205,285. Other useful ionomers aredisclosed generally in U.S. Pat. Nos. 5,631,328, 5,631,328, 5,554,698,4,801,649, 5,320,905, 5,973,046, and 4,569,865.

[0070] Ionomers comprising copolymers of ethylene derived units andacrylic acid (AA) derived units are desirable. Examples of commerciallyavailable ionomers include, but are not limited to, IOTEK ionomers(ExxonMobil Chemical Company, Houston, Tex.), such as IOTEK 8000, a 45%sodium neutralized ethylene-based ionomer of 15 wt % acrylic acid (priorto neutralization), and IOTEK 7030, a 25% zinc neutralizedethylene-based ionomer of 15 wt % acrylic acid, and SURLYN ionomers(DuPont Company, Wilmington, Del.).

[0071] The one or more ionomer layers may contain additives such asantioxidants, pigments or dyes, and other agents. In one embodiment, atleast one layer of ionomer in the final composite article will have apigment, antioxidant, or other additives. For external uses, it isdesirable to add a UV stabilizer such as TINUVEN 791 (CIBA SpecialtyChemicals) or UVASIL 2000 HM or LM (Great Lakes Chemicals), both siliconbased compositions. Also, for scratch resistance, it is advantageous toadd siloxane based compositions such as MB50-001 and/or MB50-321 (DowCorning Corporation). Effective levels are known in the art and dependon the details of the base polymers, the fabrication mode and therequirements of the end application. In addition, hydrogenated and/orpetroleum hydrocarbon resins and other plasticizers may be used asmodifiers.

[0072] Other examples of additives include one or more of the following:heat stabilizers or antioxidants, neutralizers, slip agents, antiblockagents, pigments, antifogging agents, antistatic agents, clarifiers,nucleating agents, ultraviolet absorbers or light stabilizers, fillers,rosins or rosin esters, waxes, additional plasticizers and otheradditives in conventional amounts. In one embodiment, a metallic ormetal flake pigment such as is used in the automotive industry may beused. The pigment may be included in a first, second, third ionomerlayer, or any other layer. For example, the pigment may desirably be ina second layer only, the first layer having no pigment and providinggloss and scratch resistance to the laminate. This second layer may havemetallic pigment or metal flake blend and be processed in a manner suchthat the final product has a shiny, metallic look, and changesappearance dependent upon the angle of view (“flop”) useful in, forexample, exterior automotive components, or a dull look useful in, forexample, interior automotive components.

[0073] Tie-Layer

[0074] In one embodiment, the tie-layer is made from a (co)extrudabletie resin (CTR). In another embodiment, the tie-layer may comprise oneor more layers of CTRs. In another embodiment, suitable CTRs includeblends of CTRs (as described below) and/or blends of at least one CTRwith conventional materials known in the art, i.e., acid polymers, softionomers, and thermoplastics, etc. (See WO 02/078953 and WO 02/078954).

[0075] In some of the structural formulas below, some of the bonds areshown attached to only one atom instead of two. This indicates that themoiety shown is a small segment of the whole polymer and that the freeends of those bonds are actually attached to other components of thepolymer. For simplicity, only the structure of the moiety beingdiscussed in the text is shown. One skilled in the art will understandthis shorthand notation, the types of “other components” to which thesubject moiety would be attached for the particular polymer compositionand the fact that the subject moiety might be present in many places inthe polymer.

[0076] Suitable CTRs include amine-containing polymers. Amine-containingpolymers are copolymers of one or more C₂-C₁₀ α-olefins, preferablyethylene and/or propylene, and one or more ethylenically copolymerizableamine-containing monomer, the copolymer having amine groups that may berepresented by the general formula:

[0077] where each R is independently H or a C₁ to C₁₀ hydrocarbon and R′is a bond or a C₁ to C₁₀ hydrocarbon.

[0078] In a preferred embodiment, R is H and R′ is a bond.

[0079] Other suitable CTRs include epoxy-containing copolymers andterpolymers. Epoxy-containing copolymers and terpolymers may be producedby direct copolymerization of C₂-C₁₀ α-olefins, preferably ethyleneand/or propylene, and epoxy-containing monomers such as glycidylacrylate or glycidyl methacrylate, and for terpolymers, with other estermonomers. Epoxy-containing monomers may be represented by the generalformula:

[0080] where each R is independently H or a C₁ to C₁₀ hydrocarbon and R′is independently a bond or a C₁ to C₁₀ hydrocarbon. The polymers of thisinvention may be made using mixtures of monomers with different R and R′groups.

[0081] Alternatively, epoxy-containing polymers may be made with anester monomer to form an epoxy-containing terpolymer. The ester monomermay be represented by the general formula:

[0082] where each R is independently H or a C₁ to C₁₀ hydrocarbon; eachR′ is independently a bond or a C₁ to C₁₀ hydrocarbon; and R″ is a C₁ toC₁₀ hydrocarbon. The polymers of this invention may be made usingmixtures of monomers with different R, R′ and R″ groups.

[0083] Preferred embodiments of epoxy-containing polymers include thecopolymers of ethylene and/or propylene with one or more ester monomersmethyl(meth)acrylate, ethyl(meth)acrylate, propyl(meth)acrylate, orbutyl (meth)acrylate.

[0084] Epoxy-containing polymers may also be produced by graftingepoxy-containing monomers onto C₂-C₁₀ α-olefins polymers, preferablyethylene and/or propylene polymers and/or copolymers of C₂-C₁₀ α-olefinswith polar monomers such as vinyl esters and other ester monomers. Thesegrafted, epoxy-containing polymers may be represented by the generalformula:

[0085] In some embodiments, each polymer molecule can be grafted with anepoxy-containing monomer, such as glycidyl methacrylate, in severalplaces along the polymer chain.

[0086] Preferable embodiments include glycidyl methacrylate grafted ontopolyethylene or a copolymer of ethylene with one or more ester monomersmethyl(meth)acrylate, ethyl(meth)acrylate, propyl(meth)acrylate, orbutyl (meth)acrylate.

[0087] Suitable CTRs also include acidic copolymers. Acidic copolymersinclude bipolymers of C₂-C₁₀ α-olefins, preferably ethylene and/orpropylene, and acidic monomers that may be represented by the generalformula:

[0088] where R is H or a C₁ to C₁₀ hydrocarbon and R′ is a bond or a C₁to C₁₀ hydrocarbon.

[0089] In some embodiments, the polymers of this invention may be madeusing mixtures of acid monomers with different R and R′ substituents.Preferred embodiments are ethylene and/or propylene copolymerized withacrylic acid and/or methacrylic acid.

[0090] Suitable CTRs may also be bipolymers of C₂-C₁₀ α-olefins,preferably ethylene and/or propylene, and ethylenically copolymerizableester monomers represented by the general formula:

[0091] where R is H or a C₁ to C₁₀ hydrocarbon; R′ is a bond or a C₁ toC₁₀ hydrocarbon; and R″ is a C₁ to C₁₀ hydrocarbon.

[0092] The polymers of this invention may be made using mixtures ofester monomers with different R, R′ and R″ groups. Preferred embodimentsare ethylene and/or propylene copolymerized with one or more of estermonomers methyl(meth)acrylate, ethyl(meth)acrylate,propyl(meth)acrylate, or butyl(meth)acrylate.

[0093] Suitable CTRs include copolymers of C₂-C₁₀ α-olefins, preferablyethylene and/or propylene, and vinyl ester monomers represented by theformula:

[0094] where each R is independently H or a C₁ to C₁₀ hydrocarbon.

[0095] Alternatively, vinyl ester copolymers may be made with otherester monomers to form terpolymers. The other ester monomer may berepresented by the general formula:

[0096] where R is H or a C₁ to C₁₀ hydrocarbon; R′ is a bond or a C₁ toC₁₀ hydrocarbon; and R″ is a C₁ to C₁₀ hydrocarbon.

[0097] The polymers of this invention may be made using mixtures ofvinyl ester monomers and other ester monomers with different R, R′ andR″ groups. Preferred embodiments include ethylene or propylenecopolymerized with vinyl acetate optionally with butyl(meth)acrylate.

[0098] Suitable CTRs also include grafted polymers of C₂-C₁₀ α-olefins,preferably ethylene and/or propylene, (such as LDPE, LLDPE, HDPE, PP, PPcopolymers, EPR or EPDM), ethylene vinyl ester copolymers (based on fromC₁ to C₁₀ acids), ethylene(meth)acrylate ester copolymers (made from C₁to C₁₀ alcohols) grafted with (meth)acrylic acid represented by thegeneral formula:

[0099] where each R is independently H or a C₁ to C₁₀ hydrocarbon and iis from 1 to 5. Each polymer molecule can be grafted with methacrylicacid in several places along the polymer chain.

[0100] Suitable CTRs also include polymers made with unsaturateddiacids, anhydrides of unsaturated diacids, or monoesters of unsaturateddiacids. Suitable unsaturated diacids include, but are not limited to,maleic acid, itaconic acid, citraconic acid and 2-pentenedioic acid andtheir corresponding anhydrides and monoesters. Illustrative examples maybe represented by the general formulas:

[0101] wherein for the monoester of maleic acid R is a C₁ to C₁₀hydrocarbon and wherein for the monoesters of itaconic acid, citraconicacid and 2-pentenedioic acid, either R′ is H and R″ is a C₁ to C₁₀hydrocarbon or R′ is a C₁ to C₁₀ hydrocarbon and R″ is H.

[0102] Other suitable CTRs include copolymers of one or more C₂ to C₁₀α-olefins and carbon monoxide. These copolymers may be optionallycopolymerized with one or more ethylenically copolymerizable acidic orester monomers.

[0103] Ethylenically copolymerizable acidic monomers may be representedby the general formula:

[0104] wherein R is H or a C₁ to C₁₀ hydrocarbon; R′ is a C₁ to C₁₀hydrocarbon; and n is 0 or 1. Preferred embodiments include acrylic acidand (meth)acrylic acid.

[0105] Ethylenically copolymerizable ester monomers of may berepresented by the following general formula:

[0106] wherein R is H or a C₁ to C₁₀ hydrocarbon; R′ is a C₁ to C₁₀hydrocarbon; R″ is a C₁ to C₁₀ hydrocarbon; and n is 0 or 1. Preferredembodiments include the group consisting of methyl(meth)acrylate,ethyl(meth)acrylate, propyl(meth)acrylate, and butyl(meth)acrylate.

[0107] Ethylenically copolymerizable vinyl ester monomers may berepresented by the following general formula:

[0108] wherein each R is independently H or a C₁ to C₁₀ hydrocarbon. Apreferred embodiment includes vinyl acetate.

[0109] In a preferred embodiment, the CTR is selected from the groupconsisting of an amine-containing polymer, an epoxy-containing polymer,a carbon monoxide containing polymer, a polar copolymer, a polymer madefrom an unsaturated diacid, a polymer made from a monoester of anunsaturated diacid, a polymer made from an anhydride of an unsaturateddiacid, and a polyolefin grafted with acrylic acid.

[0110] In another preferred embodiment, the CTR is selected from thegroup consisting of an amine-containing polymer, an epoxy-containingpolymer, a carbon monoxide containing polymer, an ester polymer, a vinylester polymer, a polymer made from an unsaturated diacid, a polymer madefrom a monoester of an unsaturated diacid, a polymer made from ananhydride of an unsaturated diacid, and a polyolefin grafted withacrylic acid.

[0111] CTRs useful in the invention have a melt index (MI ASTM D1238,190/2.16) of from 0.1 to 60 dg/min in one embodiment, from 0.5 to 30dg/min in another embodiment, from 1 to 20 dg/min in yet anotherembodiment, and from 2.0 to 10 dg/min in yet another embodiment , adesirable range including a combination of any upper MI limit and anylower MI limit disclosed herein.

[0112] In one embodiment, the backing layer is a blend of an appropriateCTR (selected independently from the CTR used in the tie-layer) and thematerial being used as the substrate material in the finished compositearticle. One skilled in the art will appreciate the need to selectmaterials based upon processing parameters, i.e. selecting low melt flowrates for extruding backing layers and higher melt flow rates forsubstrates that are injection molded and other parameters important forcreating a useful blend. General principles for making usefulpolymer-polymer blends can be found in the academic literature includingbooks such as Polymer Blends and Composite Articles, John A. Manson andLeslie H. Sperling, Plenum Press, New York, 1976, Polymer Blends, editedby D. R. Paul and Seymour Newman, Academic Press, New York, 1978,Specific Interactions and the Miscibility of Polymer Blends: PracticalGuides for Predicting & Designing Miscible Polymer Mixtures, Michael M.Coleman, John F. Graf, and Paul C. Painter, Technomic PublicationCompany, 1991, Polymeric Compatibilizers. Uses and Benefits in PolymerBlends, Sudhin Datta and David J. Lohse, Hanser/Gardner Publications,New York, 1996, Polymer Blends, edited by D. R. Paul and C. B. Bucknall,John Wiley & Sons, New York, 2000, and Polymer Blends Handbook, editedby L. A. Utracki, Kluwer Academic Press, Boston, 2003. The blend mayinclude from 10 wt % to 90 wt % of a CTR in the backing layer in oneembodiment, and from 20 wt % to 80 wt % in another embodiment, and from25 wt % to 65 wt % in yet another embodiment, and from 30 wt % to 50 wt% in yet another embodiment, based upon the total weight of the blend.In another embodiment, the blend comprises at least 10 wt % of a CTR,alternatively at least 15 wt %, alternatively at least 20 wt %, andalternatively at least 25 wt %, based upon the total weight of theblend. Desirable embodiments of the backing layer include anycombination of any upper CTR wt % limit and any lower CTR wt % limitdescribed herein.

[0113] The substrate materials used to blend with the at least onetie-layer material has a 1% secant flexural modulus (ASTM D-790) ofgreater than 100 MPa in one embodiment, greater than 200 MPa in anotherembodiment, greater than 300 MPa in yet another embodiment, and greaterthan 500 MPa in yet another embodiment, and greater than 900 MPa in yetanother embodiment, and less than 1000 MPa in yet another embodiment.

[0114] The tie-layer may have a thickness in the range of from 2.5 μm to6 mm in one embodiment, and from 25 μm to 650 μm in another embodiment,from 2.5 μm to 400 μm in yet another embodiment, from 2 μm to 100 μm inyet another embodiment, and from 10 μm to 1 mm in yet anotherembodiment. Desirable ranges may include any combination of any uppertie-layer thickness limit and any lower tie-layer thickness limitdescribed herein.

[0115] The tie-layer may also include additives as described above forthe ionomer layers, such as pigments, dyes, antioxidants, antiozonants,and other agents to improve its performance. Examples include one ormore of the following: heat stabilizers or antioxidants, neutralizers,slip agents, antiblock agents, pigments, antifogging agents, antistaticagents, clarifiers, nucleating agents, ultraviolet absorbers or lightstabilizers, fillers, rosins or rosin esters, waxes, additionalplasticizers and other additives in conventional amounts.

[0116] Substrate

[0117] A substrate material, as defined herein, is a material securableby any means known in the art, to the laminate. Desirably, the substrateis contacted with and secured to the tie-layer to form a compositearticle. Described another way, the substrate may be secured to thebacking layer of the tie-layer in a multi-layer embodiment. Thesubstrate material desirably has a 1% secant flexural modulus of greaterthan 100 MPa for substrate materials suitable for blending to form thebacking layer.

[0118] In one embodiment of the invention, the substrate is any“thermoplastic” material such as defined in POLYMER TECHNOLOGYDICTIONARY 443 (Tony Whelan, ed., Chapman & Hall 1994) in any form,including foams. Such materials include so called polyolefins,engineering thermoplastics, thermoplastic rubbers, elastomers, plastics,and other thermoplastics known in the art, and more particularly includesuch materials as EPDM (ethylene-propylene-diene monomer) or EP(ethylene-propylene rubber), dynamically vulcanized alloys (Santoprene™available from Advanced Elastomer Systems, Akron, Ohio),isobutylene-based rubbers (including copolymers of isobutylene andisoprene and copolymers of alkylstyrene and isobutylene, as well as thehalogenated versions of the copolymers), plastomers,acrylonitrile-butadiene-styrene terpolymer, acetal polymer, acrylicpolymers, cellulosics, fluoroplastics, nylon and other polyamides,polyamide-imide, polycarbonate, polyester, polyetheretherketone,polyetherimide, polyethylene (homopolymers and copolymers includingLLDPE, LDPE, HDPE, etc.), polyimide, polyphenylene oxide, polyphenylenesulfide, polypropylene (homopolymer, copolymers and impact copolymers(ICP)), polystyrene, polysulfone, polyurethane, polyvinyl chloride, andfoams of such materials, as well as blends of these materials and othermaterials such as described in, for example, HANDBOOK OF PLASTICS,ELASTOMERS, AND COMPOSITE ARTICLES 3.18-3.25 (Charles A. Harper, ed.,McGraw-Hill Inc. 1992). Suitable thermoplastics or blends ofthermoplastics can be made by any suitable means known in the art, andcan be made either by physical blending or in-situ reactor-made. (Seereferences on polymer blends cited above). In other embodiments, thesubstrate is not nylon(s) and/or polyamide(s); therefore, the substratedoes not contain more than 90% by weight of nylon(s) and/orpolyamide(s). However, in these embodiments, the substrate may be analloy, blend, or compound, containing nylon(s) or polyamide(s).

[0119] Desirably, in one embodiment, the substrate material has a meltflow rate (MFR) of greater than or equal to 10 dg/min (ASTM D1238,230/2.16), and greater than 20 dg/min in another embodiment and becapable of being processed such as by injection molding, or other suchprocesses described herein for securing such material to the laminate ofthe invention. For blow molding, the appropriate MI will be typicallyfrom 0.1 to 2, and in some cases less than 0.1., and other embodimentsless than 1. In some embodiments, the substrate materials have a 1%secant flexural modulus (ASTM D-790) of 100 MPa or higher.

[0120] Suitable thermoplastics include thermoplastic polyolefins such ashomopolymers, copolymers, or a combination thereof. These thermoplasticpolyolefins may be blended with the acid polymers described above and/orwith modifiers, described in greater detail below. More particularly,these thermoplastic polymers may be linear or branched polymers andinclude polyethylene polymers, polyethylene copolymers, polypropylenepolymers and polypropylene copolymers having densities in the range from0.85 to 0.96 g/cm³. Suitable comonomer reactants may include one or acombination of C₄-C₃₀ α-olefins and ethylene for use with propylene.Other useful substrate materials are the class of dynamically vulcanizedalloys of nylon and copolymers of isobutylene and p-methylstyrene.

[0121] One embodiment of a suitable substrate is a polypropylene orpolyethylene material. The polypropylene may be homopolymers, propylenebased copolymers, impact copolymers or block copolymers, or combinationsthereof. The term “polypropylene”, as used in this description and theappended claims, is defined to mean any propylene based polymer having apropylene-derived content of at least 60 wt % by weight of the“polypropylene” produced by methods well known in the art. In mostapplications it will be desirable that the polypropylene phase becontinuous or nearly continuous. The polyethylene may behomopolyethylene, ethylene based copolymers, block copolymers,plastomers, and ethylene based rubbers as is common in the art. The term“polyethylene”, as used in this description and the appended claims, isdefined to mean any ethylene based polymer having an ethylene-derivedcontent of at least 50 wt % by weight of the “polyethylene” produced bymethods well known in the art.

[0122] Other additives may be included in the substrate formulations orany other ionomer layer or tie-layer disclosed herein, as suggested bythe intended uses of the materials and the knowledge and experience ofthe formulator. In one embodiment, included in any layer is a primaryantioxidant to deter oxidative degradation of the polymer, an acidscavenger to neutralized acid catalyst residues which may be present inthe polymer to a greater or lesser extent, and nucleating agents asneeded. Examples of the former class of additives would be hinderedphenolic antioxidants and hindered amine light stabilizers, examples andthe application of which are well documented in the art. Examples of thesecond category of additives would be metal salts of weak fatty acidssuch as sodium, calcium, or zinc stearate and weakly basic, naturallyoccurring minerals such as hydrotalcite or a synthetic equivalent likeDHT-4A (Mg_(4.5)Al₂(OH)₁₃CO₃.3.5H₂0, Kiowa Chemical Industry Co., Ltd.).The listings of possible additives are meant to be illustrative but notlimiting of the choices which may be employed.

[0123] Many other types of additives could be optionally included in thelayer formulations of this invention such as flame retardants,lubricants, antistatic agents, slip agents, anti-blocking agents,colorants, metal deactivators, mold release agents, fillers andreinforcements, fluorescent whitening agents, biostabilizers, andothers.

[0124] Laminate Formation

[0125] The tie-layer and at least one ionomer layer described above maybe secured to one another by any appropriate means to form the laminate.In one embodiment, the ionomer layer is adhered to the tie-layer in acoextrusion process. The coextrusion process can include 2, 3, 4 or morecoextruded layers. In general, the process includes first melting eachmaterial in an appropriate device and extruding these molten orsemi-molten materials together through a die or dies. The various layerscan be combined in the melt stage via appropriate mechanisms known inthe art prior to exiting the die, or combined after exiting the die.This is followed by contacting the thus formed multi-layered laminatewith a series of chill rolls and sheet conveyer. The cooled laminate isthen cut to size or rolled by appropriate means. Alternatively, oneskilled in the art will appreciate that the various materials can beextruded or calendered singly and combined into a multilayer structurein a separate process.

[0126] The ionomer, CTR and other materials that form the laminate ofthe present invention can be (co)extruded using conventional equipmentwell known in the industry. In one embodiment, the extrusion processconditions are as follows. The temperature controllers of theextruder(s) used to process the ionomer(s) are set at 180° C. to 225° C.in one embodiment, yielding a final material melt temperature of 200° C.to 215° C. or higher. Desirably, the ionomer material melt temperatureis greater than 200° C. in another embodiment. The temperaturecontrollers of the extruder(s) used to process the CTR(s) are set for195° C. to 225° C. in another embodiment, yielding a final material melttemperature of 210° C. to 230° C. The viscosity of each material beingextruded should be closely matched to each other, at their respectiveprocessing temperatures, to achieve the targeted gloss level and colorcompatibility.

[0127] In a preferred embodiment, extruders are used with a die thatprovides thermal isolation and/or control of each of the materials beingprocessed to form the multilayer laminate. The temperature control canbe achieved by any suitable means such as insulation and/or coolingand/or heating elements that can be controlled by electricity, steam,oil, or other gases or liquids. Such a coextrusion apparatus isdescribed in, for example, U.S. Pat. Nos. 5,516,474 and 5,120,484, andreferences cited therein. The die may have separate flow channels withinthe die, and having a means by which to heat the material to atemperature higher than the melt temperature going into the die. Forexample, the die may be being controlled to a temperature from about150° C. to 200° C., while one or more of the material streams that willmake up the laminate may be further heated to from 230° C. to 270° C.Heating the layer having the pigment in this manner is particularlydesirable. This procedure improves the “flop” of the laminate, inparticular when metallic pigments are used such as, for example, in anexterior automotive part.

[0128] Further, the cooling of the laminate takes place on a chill rollor rolls, and may be cooled any number of ways. In one embodiment, thecooling takes place at a chill roll temperature of from 25° C. to 75° C.In yet another embodiment, the chill rolls are at from 4° C. to 20° C.In the latter embodiment, a dull finish is achieved when using ametallic pigment when the laminate is heated in the subsequentthermoforming process.

[0129] The final laminate may have any number of layers of ionomerand/or tie-layer materials. Embodiments of the laminate include onelayer of ionomer and one layer of a CTR. Another embodiment includes twolayers of ionomer and one layer of a CTR. In yet another embodiment ofthe laminate includes two layers of ionomer and two layers of tie-layermaterial such as a CTR and/or a blend of a CTR and polyolefin. In yetanother embodiment of the laminate, there may be two layers of ionomerand one layer of a CTR/polyolefin blend as the tie-layer.

[0130] In one embodiment of the laminate of the invention, two layers ofionomer may be coextruded with one layer of tie-layer material, whereinthe ionomers are Zn²⁺ and Na⁺ salts of ethylene acrylic acid copolymersand the tie-layer material is ethylene glycidyl methacrylate copolymer.Another embodiment includes two ionomer layers of zinc and sodium saltsof ethylene acrylic acid copolymers and a tie-layer including apolypropylene/ethylene butyl acrylate copolymer (EBA) blend such as, forexample, a polypropylene impact copolymer present from 10 to 90 wt % inone embodiment, and from 30 to 70 wt % in another embodiment, and from40 to 60 wt % in yet another embodiment in the blend, and EBA presentfrom 10 to 90 wt % in one embodiment, from 30 to 70 wt % in anotherembodiment, and from 40 to 60 wt % in yet another embodiment in theblend.

[0131] In yet another example of the laminate, two ionomer layers asdescribed above may be present with one layer of tie-layer material, thetie-layer including a blend of high density polyethylene (HDPE) and EBA.The HDPE may be present in the range from 10 to 90 wt % in oneembodiment, from 25 to 75 wt % in another embodiment, and from 35 to 65wt % in yet another embodiment, while the EBA is present in the rangefrom 10 to 90 wt % in one embodiment, from 25 to 75 wt % in anotherembodiment, and from 35 to 65 wt % in yet another embodiment.

[0132] In yet another example of the laminate, two ionomer layers may bepresent with one tie-layer material, wherein the tie-layer material is ablend of the following: HDPE and linear low density polyethylene (LLDPE)in a ratio of from 75/25 wt % to 85/15 wt %, blended with ethylenemethyl acrylate (EMA), the EMA present in the tie-layer blend from 10 to90 wt % in one embodiment, from 25 to 75 wt % in another embodiment, andfrom 35 to 65 wt % in yet another embodiment.

[0133] In yet another example of the laminate, two ionomer layers may bepresent with one tie-layer material, wherein the tie-layer material is ablend of the following: linear low density polyethylene blended withethylene acrylic acid (EAA), the EAA present in the tie-layer blend from10 to 90 wt % in one embodiment, from 25 to 75 wt % in anotherembodiment, and from 35 to 65 wt % in yet another embodiment.

[0134] In yet another example of the laminate, two layers of ionomer asdescribed above may be coextruded with two layers of tie-layer material.Examples of this tie-layer configuration include one layer of an EMA andanother layer of a blend of polypropylene and ethylene ethyl acrylatecopolymer (EEA), specifically, a polypropylene impact copolymer presentfrom 10 to 90 wt % in one embodiment, and from 30 to 70 wt % in anotherembodiment, and from 40 to 60 wt % in yet another embodiment in theblend, and EEA present from 10 to 90 wt % in one embodiment, from 30 to70 wt % in another embodiment, and from 40 to 60 wt % in yet anotherembodiment in the blend.

[0135] The final laminate may have any number of layers of ionomer andtie-layer materials. In one embodiment, the laminate is two layers,three in another embodiment, and four layers in yet another embodiment.In one embodiment, the ionomer layer or layers, prior to thermoforming,are from 13 μm to 1 mm. In another embodiment, the pre-thermoformedionomer layer (or layers) is from 25 μm to 380 μm. In yet anotherembodiment, the pre-thermoformed ionomer layer is from 200 μm to 380 μm.The tie-layer can be of comparable thickness ranges, making the overallthickness of the laminate from 100 μm to 5 mm in one embodiment, or from250 μm to 3 mm in yet another embodiment.

[0136] In certain embodiments, the melt viscosity, or melt indexes (MI,ASTM D1238 test method, at 190° C. and 2.16 kg load) of each adjoininglayer are within less than 5 dg/min of each other in one embodiment,within less than 4 dg/min of each other in another embodiment, and lessthan 3 dg/min from one another in yet another embodiment, and fromwithin 1 to 4 dg/min of the layer in which it is in direct contact withduring coextrusion in another embodiment, and within 2 to 3 dg/min ofone another in another embodiment. However, one skilled in the art willrecognize that the viscosity of each material to be extruded should beclosely matched to each other, at their respective processingtemperatures, to achieve the targeted gloss level and colorcompatibility.

[0137] Laminate Shaping Process

[0138] The laminate may be shaped into the profile of a desirable enduse article by any suitable means known in the art. Thermoforming,vacuum forming, and blow molding are desirable embodiments of such alaminate shaping means.

[0139] Thermoforming is a process of forming at least one pliableplastic sheet into a desired shape. Methods of thermoforming are wellknown in the art. For example, see McDonald, Joseph N., Thermoforming,ENCYCLOPEDIA OF POLYMER SCIENCE AND ENGINEERING, VOL. 16, John Wiley &Sons, 807-832 (New York 1989). In an embodiment of the presentinvention, the laminate that is formed from the at least one ionomerlayer and tie-layer are thermoformed into a desirable shape, typicallythe shape of the end use article. For illustration, an embodiment of thethermoforming sequence is described. First, a piece of the laminate, cutto the appropriate size, is placed on a shuttle rack to hold it duringheating. The shuttle rack indexes into the oven which pre-heats the filmbefore forming. Once the piece of the laminate is heated, the shuttlerack indexes back to the forming tool. The piece of the laminate is thenvacuumed onto the forming tool to hold it in place and the forming toolis closed. The forming tool can be either “male” or “female” type tools.The tool stays closed to cool the shaped laminate and the tool is thenopened. The shaped laminate is then removed from the tool.

[0140] Blow molding is another suitable laminate forming means, whichincludes injection blow molding, extrusion blow molding, and stretchblow molding. Blow molding is described in more detail in, for example,CONCISE ENCYCLOPEDIA OF POLYMER SCIENCE AND ENGINEERING 90-92(Jacqueline I. Kroschwitz, ed., John Wiley & Sons 1990). One skilled inthe art of blow molding these or similar materials will know theappropriate processing conditions to use. See, for example, WO02/078953.

[0141] Composite Article Formation

[0142] Formation of the composite article may be achieved by anysuitable means known to those skilled in the art. Illustrative examplesinclude blow molding, transfer molding, wet lay-up or contact molding,cast molding, cold forming matched-die molding, injection molding, spraytechniques, or combinations thereof. See, for example, WO 02/078953 andWO 02/078954.

[0143] In an embodiment, a (co)extruded tie-layer is secured to thepigmented ionomer layer. The material used to make the tie-layer here,and in some other embodiments of the tie-layer, may be adjusted based onthe identity of the substrate material to be used to make the finishedcomposite article. For example, if the substrate material is to be apolymer or polymer blend of polypropylene as the major component, it isdesirable for the tie-layer, or at least the backing layer of thetie-layer, to be a blend of a CTR and a polypropylene-based materialsuch as a polypropylene ICP. If the substrate material is to be apolymer or polymer blend of polyethylene as the major component, it isdesirable that the tie-layer, or at least the backing layer of thetie-layer, be a blend of a CTR and a polyethylene-based material such asa plastomer or other polyethylene.

[0144] In one embodiment, these materials are coextruded in a multilayerdie, then passed over at least two chill rolls and a sheet conveyor.This cooled sheet is then cut to size and/or wound onto a core. Sheetstaken from this cooled material can then be placed on a thermoformingrack and thermoformed to conform substantially to the shape of aninjection molding tool, followed by cooling of the shaped laminate, andtrimming of the cooled shaped laminate to prepare it for use in formingthe shaped composite article. This trimmed, shaped laminate is thenplaced into the injection molding tool exposing at least one layer ofthe tie-layer, in particular, the backing layer, in order to allow thetie-layer to be secured to the substrate material to be injected. Hence,the substrate material in molten form is then injected into the tool,forming a cohesive unit with the shaped laminate. The part that resultsis a shaped composite article having the desired shape and geometry ofthe end use article.

[0145] In an embodiment that uses the injection molding process toproduce a finished article, the shaped laminate is placed into a tooland molten substrate material is injection molded behind the laminateagainst either the backing layer or a tie-layer. The melt temperature ofthe substrate material is between 230° C. and 255° C. in one embodiment,and between 235° C. and 250° C. in another embodiment, the fill timefrom 2 to 10 seconds in one embodiment, from 2 to 8 seconds in anotherembodiment, and a tool temperature of from 25° C. to 65° C. in oneembodiment, and from 27° C. and 60° C. in another embodiment. In adesirable embodiment, the substrate material is at a temperature that ishot enough to melt the tie-layer material or backing layer to achieveadhesion between the layers.

[0146] It will be understood by those skilled in the art that the stepsoutlined above may be varied, depending upon the desired result. Forexample, the coextruded sheet of layered ionomer and tie-layer may bedirectly thermoformed or blow molded without cooling, thus skipping acooling step. Other parameters may be varied as well in order to achievea finished composite article having desirable features.

[0147] The laminate may be formed by any suitable technique such ascoextrusion, and may be shaped to form the shape of an article. Theshaping can be performed by any suitable technique such asthermoforming. Finally, the substrate may be secured to the laminate byany suitable technique such as injection molding. The thus formedcomposite article may then be used to make any number of articles.

[0148] In another embodiment, the invention is a composite articleincluding at least one layer of ionomer material, a tie-layer securableto a substrate material, and a substrate material secured to thetie-layer; the tie layer comprising at least one backing layer securedto the substrate; and wherein the backing layer comprises a blend of atleast one CTR and at least one substrate material. The at least oneionomer layer may further include both a surface layer and a sub-surfacelayer that is secured to the tie-layer. The surface ionomer layer isdesirably clear or non-pigmented and have a thickness of from 75 to 150μm, alternatively at least 100 μm. The substrate material may have a 1%secant flexural modulus of greater than 100 MPa.

[0149] The composite article thickness is typically from 1 mm to 10 mm.For example, layer thicknesses may be as follows: Ionomer Surface Layerclear: 130 μm-380 μm Ionomer Sub-surface Layer pigmented: 130 μm-640 μmCTR-Based Tie-Layer pigmented or natural color: 25 μm-250 μm BackingLayer pigmented or natural color: 250 μm-1 mm Substrate pigmented ornatural color: 2 mm-6 mm

[0150] Industrial Applications

[0151] The laminates and composite articles of the present invention canbe used in various applications. They may be used in interior andexterior components of appliances such as clothing or dish washerexteriors, refrigerator door exteriors, refrigerator door interiors,refrigerator liners, refrigerator housings.

[0152] The laminates and composite articles of the present invention canalso be applied in construction. Some examples include tubs and showers,liners for tubs and showers, counter tops, floor coatings, laminatedsurface counter tops, polymer/wood composites, prefabricated buildingmaterials, sidings, sinks and sink liners, synthetic marble panels,translucent glass replacements, vinyl tiles, wall covering, and woodreplacements for decks.

[0153] Additionally, the laminates and composite articles of the presentinvention have utility in electronics for CDs and DVDs as well as forhousing on TVs, VCRs, computers, and stereos.

[0154] The laminates and composite articles of the present invention mayalso be used in a variety of sporting equipment and parts. Illustrativeexamples include boats, hulls, boat hulls, marine boat hulls, canoeinteriors and exteriors, boat covers, boat sails, jet skis (housings),skis, snowboards, snowmobiles, sports helmets, stadium seats,surfboards, and tent materials.

[0155] In other applications, the present invention is applied toexterior or interior automotive parts. Illustrative examples includevehicular parts, automotive parts, airbag doors, doors, automotive doorpanels (interior and exterior), body chassis, body panels, bumpers, decklids, fenders, hoods, rocker panels, mirror housings, dashboards,instrument panels, fuel tanks, grills, hopper cars, interior trims,pillar trims, cup holders, personal containers, and wheel covers.Applications within this category also include other minor components ofany 2, 3, 4 or more wheeled vehicles including farm tractors; lawn andgarden tractors; lawn mowers; large trucks; bicycles; toy wagons; partsfor All Terrain Vehicles (ATVs); parts for motorcycles such as fueltanks; scooters; seat covers; and trims.

[0156] The inventive laminates and composite articles may be used inlawn, yard, and garden applications as well. Some examples arelawn/outdoor furniture, pool liners and covers, outdoor ornaments, andbird houses.

[0157] The inventive laminates and composite articles may also be usedin aerospace reentry shields, cable jacketing, children's toys,clothing/fabric (combined with non-wovens), Gamma-radiation resistantapplications, GORETEX™, luggage, and other applications for coatingplastics and metals where a dull or glossy and a scratch resistantsurface is desirable such as plastic microwaveable cookware, plasticpaper goods, reflective signage and other reflective articles on roadsand clothing, and wheels on in-line skates.

[0158] The aforementioned industrial applications may be combined withany of the embodiments described in the SUMMARY as well as anyembodiments as claimed.

[0159] While the present invention has been described and illustrated byreference to particular embodiments, those of ordinary skill in the artwill appreciate that the invention lends itself to many differentvariations not illustrated herein. For these reasons, then, referenceshould be made solely to the appended claims for purposes of determiningthe true scope of the present invention.

[0160] Terms that are or may be trademarked in some jurisdictions areused in the description. These terms are written in all capital letters,and is understood to recognize such trademarks. For brevity, markingssuch as “™” or “®” have not been used.

[0161] All priority documents are herein fully incorporated by referencefor all jurisdictions in which such incorporation is permitted. Further,all documents cited herein, including testing procedures, publications,patents, journal articles, etc., are herein fully incorporated byreference for all jurisdictions in which such incorporation ispermitted.

What is claimed is:
 1. A laminate comprising: an ionomer layer and atie-layer comprising a (co)extrudable tie resin (CTR).
 2. The laminateof claim 1, wherein the CTR comprises a copolymer of one or more C₂-C₁₀α-olefins and one or more ethylenically copolymerizable amine-containingmonomers, the copolymer having amine groups that may be represented bythe general formula:

where each R is independently H or a C₁ to C₁₀ hydrocarbon and R′ is abond or a C₁ to C₁₀ hydrocarbon.
 3. The laminate of claim 2, wherein Ris H and R′ is a bond.
 4. The laminate of claim 2, wherein the C₂-C₁₀α-olefins are ethylene and/or propylene.
 5. The laminate of claim 1,wherein the CTR comprises an epoxy-containing polymer comprising acopolymer of C₂-C₁₀ α-olefins and epoxy-containing monomers.
 6. Thelaminate of claim 5, wherein the epoxy-containing monomer is representedby the general formula:

where each R is independently H or a C₁ to C₁₀ hydrocarbon and R′ isindependently a bond or a C₁ to C₁₀ hydrocarbon.
 7. The laminate ofclaim 5, wherein the C₂-C₁₀ α-olefins are ethylene and/or propylene. 8.The laminate of claim 5, wherein the epoxy-containing monomers areselected from the group consisting of glycidyl acrylate and glycidylmethacrylate.
 9. The laminate of claim 5, wherein the copolymer furthercomprises an ester monomer represented by the general formula:

where each R is independently H or a C₁ to C₁₀ hydrocarbon; each R′ isindependently a bond or a C₁ to C₁₀ hydrocarbon; and R″ is a C₁ to C₁₀hydrocarbon.
 10. The laminate of claim 9, wherein the ester monomer isselected from the group consisting of methyl(meth)acrylate,ethyl(meth)acrylate, propyl(meth)acrylate, and butyl(meth)acrylate. 11.The laminate of claim 1, wherein the CTR comprises a grafted,epoxy-containing polymer represented by the general formula:


12. The laminate of claim 1, wherein the CTR comprises a grafted,epoxy-containing polymer produced by grafting epoxy-containing monomersonto C₂-C₁₀ α-olefins polymers.
 13. The laminate of claim 12, where theC₂-C₁₀ α-olefins polymers are ethylene and/or propylene polymers. 14.The laminate of claim 1, wherein the CTR comprises an epoxy-containingpolymer, the epoxy-containing polymer comprising glycidyl methacrylategrafted onto polyethylene or a copolymer of ethylene with one or moreester monomers selected from the group consisting ofmethyl(meth)acrylate, ethyl(meth)acrylate, propyl(meth)acrylate andbutyl(meth)acrylate.
 15. The laminate of claim 1, wherein the CTRcomprises an acidic copolymer.
 16. The laminate of claim 14, wherein theacidic copolymer is a bipolymer of C₂-C₁₀ α-olefins and acidic monomersrepresented by the general formula:

where R is H or a C₁ to C₁₀ hydrocarbon and R′ is a bond or a C₁ to C₁₀hydrocarbon.
 17. The laminate of claim 16, where the C₂-C₁₀ α-olefinsare ethylene and/or propylene.
 18. The laminate of claim 15, wherein theacidic copolymer is a bipolymer of ethylene and/or propylene and acrylicacid and/or methacrylic acid.
 19. The laminate of claim 1, where the CTRcomprises a bipolymer of C₂-C₁₀ α-olefins and ethylenicallycopolymerizable ester monomers represented by the general formula:

where R is H or a C₁ to C₁₀ hydrocarbon; R′ is a bond or a C₁ to C₁₀hydrocarbon; and R″ is a C₁ to C₁₀ hydrocarbon.
 20. The laminate ofclaim 19, where the C₂-C₁₀ α-olefins are ethylene and/or propylene. 21.The laminate of claim 19, wherein the ester monomer is selected from thegroup consisting of methyl(meth)acrylate, ethyl(meth)acrylate,propyl(meth)acrylate, and butyl(meth)acrylate.
 22. The laminate of claim1, wherein the CTR comprises a copolymer of C₂-C₁₀ α-olefins and vinylester monomers represented by the formula:

where each R is independently H or a C₁ to C₁₀ hydrocarbon.
 23. Thelaminate of claim 22, wherein the C₂-C₁₀ α-olefins are ethylene and/orpropylene.
 24. The laminate of claim 22, wherein the copolymer furthercomprises another ester monomer, the another ester monomer representedby the general formula:

wherein R is H or a C₁ to C₁₀ hydrocarbon; R′ is a bond or a C₁ to C₁₀hydrocarbon; and R″ is a C₁ to C₁₀ hydrocarbon.
 25. The laminate ofclaim 1, wherein the CTR comprises a copolymer of ethylene and/orpropylene and vinyl acetate, optionally copolymerized withbutyl(meth)acrylate.
 26. The laminate of claim 1, wherein the CTRcomprises grafted polymers of C₂-C₁₀ α-olefins, ethylene vinyl estercopolymers (based on from C₁ to C₁₀ acids), ethylene(meth)acrylate estercopolymers (made from C₁ to C₁₀ alcohols) and a (meth)acrylic acidgroup, the (meth)acrylic acid group represented by the general formula:

where each R is independently H or a C₁ to C₁₀ hydrocarbon and i is from1 to
 5. 27. The laminate of claim 26, wherein the C₂-C₁₀ α-olefins areethylene and/or propylene.
 28. The laminate of claim 1, wherein the CTRcomprises a polymer made with an unsaturated diacid.
 29. The laminate ofclaim 28, wherein the unsaturated diacid is selected from the groupconsisting of maleic acid, itaconic acid, citraconic acid, and2-pentenedioic acid.
 30. The laminate of claim 1, wherein the CTRcomprises a polymer made with an anhydride of an unsaturated diacid. 31.The laminate of claim 30, the anhydride is selected from the groupconsisting of maleic anhydride, itaconic anhydride, citraconicanhydride, and 2-pentendioic anhydride.
 32. The laminate of claim 1,wherein the CTR comprises a polymer made with a monoester of anunsaturated diacid.
 33. The laminate of claim 32, wherein the monoesteris selected from the group consisting of a monoester of maleic acid, amonoester of itaconic acid, a monoester of citraconic acid, and amonoester of 2-pentenedioic acid.
 34. The laminate of claim 1, whereinthe CTR is selected from the group consisting of an amine-containingpolymer, an epoxy-containing polymer, a polar copolymer, a polymer madefrom an unsaturated diacid, a polymer made from a monoester of anunsaturated diacid, a polymer made from an anhydride of an unsaturateddiacid, and a polyolefin grafted with (meth)acrylic acid.
 35. Thelaminate of claim 1, wherein the CTR is selected from the groupconsisting of an amine-containing polymer, an epoxy-containing polymer,an ester polymer, a vinyl ester polymer, a polymer made from anunsaturated diacid, a polymer made from a monoester of an unsaturateddiacid, a polymer made from an anhydride of an unsaturated diacid, and apolyolefin grafted with (meth)acrylic acid.
 36. The laminate of claim 1,wherein the tie-layer comprises a blend of a maleated polypropylene andan acid polymer.
 37. The laminate of claim 1, wherein the CTR comprisesa copolymer of one or more C₂ to C₁₀ α-olefins and carbon monoxide. 38.The laminate of claim 37, wherein the copolymer is further copolymerizedwith one or more ethylenically copolymerizable acidic monomersrepresented by the general formula:

wherein R is H or a C₁ to C₁₀ hydrocarbon; R′ is a C₁ to C₁₀hydrocarbon; and n is 0 or
 1. 39. The laminate of claim 37, wherein thecopolymer is copolymerized with one or more ester monomers representedby the general formula:

wherein R is H or a C₁ to C₁₀ hydrocarbon; R′ is a C₁ to C₁₀hydrocarbon; R″ is a C₁ to C₁₀ hydrocarbon; and n is 0 or 1; or

wherein each R is independently H or a C₁ to C₁₀ hydrocarbon.
 40. Thelaminate of claim 1, wherein the ionomer layer comprises a first ionomerlayer and a second ionomer layer.
 41. The laminate of claim 15, whereinthe first ionomer layer or the second ionomer layer is pigmented,natural, or clear.
 42. The laminate of claim 1, further comprising abacking layer.
 43. A composite comprising: an ionomer layer; a tie-layercomprising a (co) extrudable tie resin (CTR); and a substrate.
 44. Thecomposite of claim 43, wherein the CTR comprises a copolymer of one ormore C₂-C₁₀ α-olefins and one or more ethylenically copolymerizableamine-containing monomers, the copolymer having amine groups that may berepresented by the general formula:

where each R is independently H or a C₁ to C₁₀ hydrocarbon and R′ is abond or a C₁ to C₁₀ hydrocarbon.
 45. The composite of claim 44, whereinR is H and R′ is a bond.
 46. The composite of claim 44, wherein theC₂-C₁₀ α-olefins are ethylene and/or propylene.
 47. The composite ofclaim 43, wherein the CTR comprises an epoxy-containing polymercomprising a copolymer of C₂-C₁₀ α-olefins and epoxy-containingmonomers.
 48. The composite of claim 47, wherein the epoxy-containingmonomer is represented by the general formula:

where each R is independently H or a C₁ to C₁₀ hydrocarbon and R′ isindependently a bond or a C₁ to C₁₀ hydrocarbon.
 49. The composite ofclaim 47, wherein the C₂-C₁₀ α-olefins are ethylene and/or propylene.50. The composite of claim 47, wherein the epoxy-containing monomers areselected from the group consisting of glycidyl acrylate and glycidylmethacrylate.
 51. The composite of claim 47, wherein the copolymerfurther comprises an ester monomer represented by the general formula:

where each R is independently H or a C₁ to C₁₀ hydrocarbon; each R′ isindependently a bond or a C₁ to C₁₀ hydrocarbon; and R″ is a C₁ to C₁₀hydrocarbon.
 52. The composite of claim 51, wherein the ester monomer isselected from the group consisting of methyl(meth)acrylate,ethyl(meth)acrylate, propyl(meth)acrylate, and butyl(meth)acrylate. 53.The composite of claim 43, wherein the CTR comprises a grafted,epoxy-containing polymer represented by the general formula:


54. The composite of claim 43, wherein the CTR comprises a grafted,epoxy-containing polymer produced by grafting epoxy-containing monomersonto C₂-C₁₀ α-olefins polymers.
 55. The composite of claim 54, where theC₂-C₁₀ α-olefins polymers are ethylene and/or propylene polymers. 56.The composite of claim 43, wherein the CTR comprises an epoxy-containingpolymer, the epoxy-containing polymer comprising glycidyl methacrylategrafted onto polyethylene or a copolymer of ethylene with one or moreester monomers selected from the group consisting ofmethyl(meth)acrylate, ethyl(meth)acrylate, propyl(meth)acrylate andbutyl(meth)acrylate.
 57. The composite of claim 43, wherein the CTRcomprises an acidic copolymers.
 58. The composite of claim 57, whereinthe acidic copolymer is a bipolymer of C₂-C₁₀ α-olefins and acidicmonomers represented by the general formula:

where R is H or a C₁ to C₁₀ hydrocarbon and R′ is a bond or a C₁ to C₁₀hydrocarbon.
 59. The composite of claim 58, where the C₂-C₁₀ α-olefinsare ethylene and/or propylene.
 60. The composite of claim 57, whereinthe acidic copolymer is a bipolymer of ethylene and/or propylene andacrylic acid and/or methacrylic acid.
 61. The composite of claim 43,where the CTR comprises a bipolymer of C₂-C₁₀ α-olefins andethylenically copolymerizable ester monomers represented by the generalformula:

where R is H or a C₁ to C₁₀ hydrocarbon; R′ is a bond or a C₁ to C₁₀hydrocarbon; and R″ is a C₁ to C₁₀ hydrocarbon.
 62. The composite ofclaim 61, where the C₂-C₁₀ α-olefins are ethylene and/or propylene. 63.The composite of claim 61, wherein the ester monomer is selected fromthe group consisting of methyl(meth)acrylate, ethyl(meth)acrylate,propyl(meth)acrylate, and butyl(meth)acrylate.
 64. The composite ofclaim 43, wherein the CTR comprises a copolymer of C₂-C₁₀ α-olefins andvinyl ester monomers represented by the formula:

where each R is independently H or a C₁ to C₁₀ hydrocarbon.
 65. Thecomposite of claim 64, wherein the C₂-C₁₀ α-olefins are ethylene and/orpropylene.
 66. The composite of claim 64, wherein the copolymer furthercomprises another ester monomer, the another ester monomer representedby the general formula:

where each R is independently H or a C₁ to C₁₀ hydrocarbon; R′ is a bondor a C₁ to C₁₀ hydrocarbon; and R″ is a C₁ to C₁₀ hydrocarbon.
 67. Thecomposite of claim 43, wherein the CTR comprises a copolymer of ethyleneand/or propylene and vinyl acetate, optionally copolymerized withbutyl(meth)acrylate.
 68. The composite of claim 43, wherein the CTRcomprises grafted polymers of C₂-C₁₀ α-olefins, ethylene vinyl estercopolymers (based on from C₁ to C₁₀ acids), ethylene(meth)acrylate estercopolymers (made from C₁ to C₁₀ alcohols) and a (meth)acrylic acidgroup, the (meth)acrylic acid group represented by the general formula:

where each R is independently H or a C₁ to C₁₀ hydrocarbon and i is from1 to
 5. 69. The composite of claim 68, wherein the C₂-C₁₀ α-olefins areethylene and/or propylene.
 70. The composite of claim 43, wherein theCTR comprises a polymer made with an unsaturated diacid.
 71. Thecomposite of claim 69, wherein the unsaturated diacid is selected fromthe group consisting of maleic acid, itaconic acid, citraconic acid, and2-pentenedioic acid.
 72. The composite of claim 43, wherein the CTRcomprises a polymer made with an anhydride of an unsaturated diacid. 73.The composite of claim 72, the anhydride is selected from the groupconsisting of maleic anhydride, itaconic anhydride, citraconicanhydride, and 2-pentendioic anhydride.
 74. The composite of claim 43,wherein the CTR comprises a polymer made with a monoester of anunsaturated diacid.
 75. The composite of claim 74, wherein the monoesteris selected from the group consisting of a monoester of maleic acid, amonoester of itaconic acid, a monoester of citraconic acid, and amonoester of 2-pentenedioic acid.
 76. The composite of claim 43, whereinthe CTR is selected from the group consisting of an amine-containingpolymer, an epoxy-containing polymer, a polar copolymer, a polymer madefrom an unsaturated diacid, a polymer made from a monoester of anunsaturated diacid, a polymer made from an anhydride of an unsaturateddiacid, and a polyolefin grafted with(meth)acrylic acid.
 77. Thecomposite of claim 43, wherein the CTR is selected from the groupconsisting of an amine-containing polymer, an epoxy-containing polymer,an ester polymer, a vinyl ester polymer, a polymer made from anunsaturated diacid, a polymer made from a monoester of an unsaturateddiacid, a polymer made from an anhydride of an unsaturated diacid, and apolyolefin grafted with (meth)acrylic acid.
 78. The composite of claim43, wherein the tie-layer comprises a blend of a maleated polypropyleneand an acid polymer.
 79. The composite of claim 43, wherein the CTRcomprises a copolymer of one or more C₂ to C₁₀ α-olefins and carbonmonoxide.
 80. The composite of claim 79, wherein the copolymer isfurther copolymerized with one or more ethylenically copolymerizableacidic monomers represented by the general formula:

wherein R is H or a C₁ to C₁₀ hydrocarbon; R′ is a C₁ to C₁₀hydrocarbon; and n is 0 or
 1. 81. The composite of claim 79, wherein thecopolymer is copolymerized with one or more ester monomers representedby the general formula:

wherein R is H or a C₁ to C₁₀ hydrocarbon; R′ is a C₁ to C₁₀hydrocarbon; R″ is a C₁ to C₁₀ hydrocarbon; and n is 0 or 1; or

wherein each R is independently H or a C₁ to C₁₀ hydrocarbon.
 82. Thecomposite of claim 43, wherein the ionomer layer comprises a firstionomer layer and a second ionomer layer.
 83. The composite of claim 82,wherein the first ionomer layer or the second ionomer layer ispigmented, natural, or clear.
 84. The composite of claim 43, wherein theionomer layer comprises a zinc-neutralized ionomer or asodium-neutralized ionomer.
 85. The composite of claim 43, furthercomprising a backing layer.
 86. The composite of claim 43, wherein thethickness of the composite article is from 200 μm to 6 mm.
 87. Thecomposite of claim 43, wherein the substrate material is selected fromEPDM (ethylene-propylene-diene monomer), EP (ethylene-propylene rubber),acrylonitrile-butadiene-styrene terpolymer, acetal polymer, acrylicpolymers, cellulosics, fluoroplastics, nylon and other polyamides,polyamide-imide, polycarbonate, polyester, polyetheretherketone,polyetherimide, polyethylene, polyimide, polyphenylene, polyphenylenesulfide, plastomer, polypropylene, polypropylene impact copolymers,polystyrene, polysulfone, polyurethane, polyvinyl chloride, and foams ofsuch materials, as well as blends of these materials.
 88. The compositeof claim 43, wherein the substrate is a polyolefin selected frompolyethylene polymers, polyethylene copolymers, polypropylene polymers,polypropylene copolymers, polypropylene impact copolymer and a blend ofpolypropylene impact copolymer and ethylene plastomer, and mixturesthereof.
 89. A composite article comprising: a) an ionomer layer; b) atie-layer comprising a (co) extrudable tie resin (CTR); c) a backinglayer; and d) a substrate.
 90. The composite article of claim 88,wherein the CTR comprises a copolymer of one or more C₂-C₁₀ α-olefinsand one or more ethylenically copolymerizable amine-containing monomers,the copolymer having amine groups that may be represented by the generalformula:

where each R is independently H or a C₁ to C₁₀ hydrocarbon and R′ is abond or a C₁ to C₁₀ hydrocarbon.
 91. The composite article of claim 90,wherein R is H and R′ is a bond.
 92. The composite article of claim 90,wherein the C₂-C₁₀ α-olefins are ethylene and/or propylene.
 93. Thecomposite article of claim 89, wherein the CTR comprises anepoxy-containing polymer comprising a copolymer of C₂-C₁₀ α-olefins andepoxy-containing monomers.
 94. The composite article of claim 93,wherein the epoxy-containing monomer is represented by the generalformula:

where each R is independently H or a C₁ to C₁₀ hydrocarbon and R′ isindependently a bond or a C₁ to C₁₀ hydrocarbon.
 95. The compositearticle of claim 93, wherein the C₂-C₁₀ α-olefins are ethylene and/orpropylene.
 96. The composite article of claim 93, wherein theepoxy-containing monomers are selected from the group consisting ofglycidyl acrylate and glycidyl methacrylate.
 97. The composite articleof claim 93, wherein the copolymer further comprises an ester monomerrepresented by the general formula:

where each R is independently H or a C₁ to C₁₀ hydrocarbon; each R′ isindependently a bond or a C₁ to C₁₀ hydrocarbon; and R″ is a C₁ to C₁₀hydrocarbon.
 98. The composite article of claim 97, wherein the estermonomer is selected from the group consisting of methyl (meth)acrylate,ethyl(meth)acrylate, propyl(meth)acrylate, and butyl(meth)acrylate. 99.The composite article of claim 89, wherein the CTR comprises a grafted,epoxy-containing polymer represented by the general formula:


100. The composite article of claim 89, wherein the CTR comprises agrafted, epoxy-containing polymer produced by grafting epoxy-containingmonomers onto C₂-C₁₀ α-olefins polymers.
 101. The composite article ofclaim 100, where the C₂-C₁₀ α-olefins polymers are ethylene and/orpropylene polymers.
 102. The composite article of claim 89, wherein theCTR comprises an epoxy-containing polymer, the epoxy-containing polymercomprising glycidyl methacrylate grafted onto polyethylene or acopolymer of ethylene with one or more ester monomers selected from thegroup consisting of methyl(meth)acrylate, ethyl(meth)acrylate,propyl(meth)acrylate and butyl(meth)acrylate.
 103. The composite articleof claim 89, wherein the CTR comprises an acidic copolymers.
 104. Thecomposite article of claim 103, wherein the acidic copolymer is abipolymer of C₂-C₁₀ α-olefins and acidic monomers represented by thegeneral formula:

where R is H or a C₁ to C₁₀ hydrocarbon and R′ is a bond or a C₁ to C₁₀hydrocarbon.
 105. The composite article of claim 104, where the C₂-C₁₀α-olefins are ethylene and/or propylene.
 106. The composite article ofclaim 103, wherein the acidic copolymer is a bipolymer of ethyleneand/or propylene and acrylic acid and/or methacrylic acid.
 107. Thecomposite article of claim 89, where the CTR comprises a bipolymer ofC₂-C₁₀ α-olefins and ethylenically copolymerizable ester monomersrepresented by the general formula:

where R is H or a C₁ to C₁₀ hydrocarbon; R′ is a bond or a C₁ to C₁₀hydrocarbon; and R″ is a C₁ to C₁₀ hydrocarbon.
 108. The compositearticle of claim 107, where the C₂-C₁₀ α-olefins are ethylene and/orpropylene.
 109. The composite article of claim 107, wherein the estermonomer is selected from the group consisting of methyl(meth)acrylate,ethyl(meth)acrylate, propyl(meth)acrylate, and butyl(meth)acrylate. 110.The composite article of claim 89, wherein the CTR comprises a copolymerof C₂-C₁₀ α-olefins and vinyl ester monomers represented by the formula:

where each R is independently H or a C₁ to C₁₀ hydrocarbon.
 111. Thecomposite article of claim 110, wherein the C₂-C₁₀ α-olefins areethylene and/or propylene.
 112. The composite article of claim 110,wherein the copolymer further comprises another ester monomer, theanother ester monomer represented by the general formula:

where each R is independently H or a C₁ to C₁₀ hydrocarbon; R′ is a bondor a C₁ to C₁₀ hydrocarbon; and R″ is a C₁ to C₁₀ hydrocarbon.
 113. Thecomposite article of claim 89, wherein the CTR comprises a copolymer ofethylene and/or propylene and vinyl acetate, optionally copolymerizedwith butyl(meth)acrylate.
 114. The composite article of claim 89,wherein the CTR comprises grafted polymers of C₂-C₁₀ α-olefins, ethylenevinyl ester copolymers (based on from C₁ to C₁₀ acids),ethylene(meth)acrylate ester copolymers (made from C₁ to C₁₀ alcohols)and a (meth)acrylic acid group, the (meth)acrylic acid group representedby the general formula:

where each R is independently H or a C₁ to C₁₀ hydrocarbon and i is from1 to
 5. 115. The composite article of claim 114, wherein the C₂-C₁₀α-olefins are ethylene and/or propylene.
 116. The composite article ofclaim 89, wherein the CTR comprises a polymer made with an unsaturateddiacid.
 117. The composite article of claim 116, wherein the unsaturateddiacid is selected from the group consisting of maleic acid, itaconicacid, citraconic acid, and 2-pentenedioic acid.
 118. The compositearticle of claim 89, wherein the CTR comprises a polymer made with ananhydride of an unsaturated diacid.
 119. The composite article of claim118, the anhydride is selected from the group consisting of maleicanhydride, itaconic anhydride, citraconic anhydride, and 2-pentendioicanhydride.
 120. The composite article of claim 89, wherein the CTRcomprises a polymer made with a monoester of an unsaturated diacid. 121.The composite article of claim 120, wherein the monoester is selectedfrom the group consisting of a monoester of maleic acid, a monoester ofitaconic acid, a monoester of citraconic acid, and a monoester of2-pentenedioic acid.
 122. The composite article of claim 89, wherein theCTR is selected from the group consisting of an amine-containingpolymer, an epoxy-containing polymer, a polar copolymer, a polymer madefrom an unsaturated diacid, a polymer made from a monoester of anunsaturated diacid, a polymer made from an anhydride of an unsaturateddiacid, and a polyolefin grafted with(meth)acrylic acid.
 123. Thecomposite article of claim 89, wherein the CTR is selected from thegroup consisting of an amine-containing polymer, an epoxy-containingpolymer, an ester polymer, a vinyl ester polymer, a polymer made from anunsaturated diacid, a polymer made from a monoester of an unsaturateddiacid, a polymer made from an anhydride of an unsaturated diacid, and apolyolefin grafted with (meth)acrylic acid.
 124. The composite articleof claim 89, wherein the tie-layer comprises a blend of a maleatedpolypropylene and an acid polymer.
 125. The composite article of claim89, wherein the CTR comprises a copolymer of one or more C₂ to C₁₀α-olefins and carbon monoxide.
 126. The composite article of claim 125,wherein the copolymer is further copolymerized with one or moreethylenically copolymerizable acidic monomers represented by the generalformula:

wherein R is H or a C₁ to C₁₀ hydrocarbon; R′ is a C₁ to C₁₀hydrocarbon; and n is 0 or
 1. 127. The composite article of claim 125,wherein the copolymer is copolymerized with one or more ester monomersrepresented by the general formula:

wherein R is H or a C₁ to C₁₀ hydrocarbon; R′ is a C₁ to C₁₀hydrocarbon; R″ is a C₁ to C₁₀ hydrocarbon; and n is 0 or 1; or

wherein each R is independently H or a C₁ to C₁₀ hydrocarbon.
 128. Thecomposite article of claim 89, wherein the ionomer layer comprises afirst ionomer layer and a second ionomer layer.
 129. The compositearticle of claim 128, wherein the first ionomer layer or the secondionomer layer is pigmented, natural, or clear.
 130. The compositearticle of claim 89, wherein the ionomer layer comprises azinc-neutralized ionomer or a sodium-neutralized ionomer.
 131. Thecomposite article of claim 89, further comprising a backing layer. 132.The composite article of claim 89, wherein the thickness of thecomposite article is from 200 μm to 6 mm.
 133. The composite article ofclaim 89, wherein the substrate material is selected from EPDM(ethylene-propylene-diene monomer), EP (ethylene-propylene rubber),acrylonitrile-butadiene-styrene terpolymer, acetal polymer, acrylicpolymers, cellulosics, fluoroplastics, nylon and other polyamides,polyamide-imide, polycarbonate, polyester, polyetheretherketone,polyetherimide, polyethylene, polyimide, polyphenylene, polyphenylenesulfide, plastomer, polypropylene, polypropylene impact copolymers,polystyrene, polysulfone, polyurethane, polyvinyl chloride, and foams ofsuch materials, as well as blends of these materials.
 134. The compositearticle of claim 89, wherein the substrate is a polyolefin selected frompolyethylene polymers, polyethylene copolymers, polypropylene polymers,polypropylene copolymers, polypropylene impact copolymer and a blend ofpolypropylene impact copolymer and ethylene plastomer, and mixturesthereof.
 135. A method of forming a composite article comprising: (a)providing a laminate comprising an ionomer layer and a tie-layer, thetie-layer comprising a (co) extrudable tie resin (CTR); and (b) securinga substrate to the tie-layer of the laminate to form the compositearticle.
 136. The method of claim 135, wherein the CTR comprises acopolymer of one or more C₂-C₁₀ α-olefins and one or more ethylenicallycopolymerizable amine-containing monomers, the copolymer having aminegroups that may be represented by the general formula:

where each R is independently H or a C₁ to C₁₀ hydrocarbon and R′ is abond or a C₁ to C₁₀ hydrocarbon.
 137. The method of claim 136, wherein Ris H and R′ is a bond.
 138. The method of claim 136, wherein the C₂-C₁₀α-olefins are ethylene and/or propylene.
 139. The method of claim 1,wherein the CTR comprises an epoxy-containing polymer comprising acopolymer of C₂-C₁₀ α-olefins and epoxy-containing monomers.
 140. Themethod of claim 139, wherein the epoxy-containing monomer is representedby the general formula:

where each R is independently H or a C₁ to C₁₀ hydrocarbon and R′ isindependently a bond or a C₁ to C₁₀ hydrocarbon.
 141. The method ofclaim 139, wherein the C₂-C₁₀ α-olefins are ethylene and/or propylene.142. The method of claim 139 wherein the epoxy-containing monomers areselected from the group consisting of glycidyl acrylate and glycidylmethacrylate.
 143. The method of claim 139, wherein the copolymerfurther comprises an ester monomer represented by the general formula:

where each R is independently H or a C₁ to C₁₀ hydrocarbon; each R′ isindependently a bond or a C₁ to C₁₀ hydrocarbon; and R″ is a C₁ to C₁₀hydrocarbon.
 144. The method of claim 143, wherein the ester monomer isselected from the group consisting of methyl(meth)acrylate,ethyl(meth)acrylate, propyl(meth)acrylate, and butyl(meth)acrylate. 145.The method of claim 135, wherein the CTR comprises a grafted,epoxy-containing polymer represented by the general formula:


146. The method of claim 135, wherein the CTR comprises a grafted,epoxy-containing polymer produced by grafting epoxy-containing monomersonto C₂-C₁₀ α-olefins polymers.
 147. The method of claim 146, where theC₂-C₁₀ α-olefins polymers are ethylene and/or propylene polymers. 148.The method of claim 135, wherein the CTR comprises an epoxy-containingpolymer, the epoxy-containing polymer comprising glycidyl methacrylategrafted onto polyethylene or a copolymer of ethylene with one or moreester monomers selected from the group consisting ofmethyl(meth)acrylate, ethyl(meth)acrylate, propyl(meth)acrylate andbutyl(meth)acrylate.
 149. The method of claim 135, wherein the CTRcomprises an acidic copolymers.
 150. The method of claim 149, whereinthe acidic copolymer is a bipolymer of C₂-C₁₀ α-olefins and acidicmonomers represented by the general formula:

where R is H or a C₁ to C₁₀ hydrocarbon and R′ is a bond or a C₁ to C₁₀hydrocarbon.
 151. The method of claim 150, where the C₂-C₁₀ α-olefinsare ethylene and/or propylene.
 152. The method of claim 149, wherein theacidic copolymer is a bipolymer of ethylene and/or propylene and acrylicacid and/or methacrylic acid.
 153. The method of claim 135, where theCTR comprises a bipolymer of C₂-C₁₀ α-olefins and ethylenicallycopolymerizable ester monomers represented by the general formula:

where R is H or a C₁ to C₁₀ hydrocarbon; R′ is a bond or a C₁ to C₁₀hydrocarbon; and R″ is a C₁ to C₁₀ hydrocarbon.
 154. The method of claim153, where the C₂-C₁₀ α-olefins are ethylene and/or propylene.
 155. Themethod of claim 153, wherein the CTR ester monomer is selected from thegroup consisting of methyl(meth)acrylate, ethyl (meth)acrylate,propyl(meth)acrylate, and butyl(meth)acrylate.
 156. The method of claim135, wherein the CTR comprises a copolymer of C₂-C₁₀ α-olefins and vinylester monomers, represented by the formula:

where each R is independently H or a C₁ to C₁₀ hydrocarbon.
 157. Themethod of claim 156, wherein the C₂-C₁₀ α-olefins are ethylene and/orpropylene.
 158. The method of claim 156, wherein the copolymer furthercomprises another ester monomer, the another ester monomer representedby the general formula:

where each R is independently H or a C₁ to C₁₀ hydrocarbon; R′ is a bondor a C₁ to C₁₀ hydrocarbon; and R″ is a C₁ to C₁₀ hydrocarbon.
 159. Themethod of claim 135, wherein the CTR comprises a copolymer of ethyleneand/or propylene and vinyl acetate, optionally copolymerized withbutyl(meth)acrylate.
 160. The method of claim 135, wherein the CTRcomprises grafted polymers of C₂-C₁₀ α-olefins, ethylene vinyl estercopolymers (based on from C₁ to C₁₀ acids), ethylene(meth)acrylate estercopolymers (made from C₁ to C₁₀ alcohols) and a (meth)acrylic acidgroup, the (meth)acrylic acid group represented by the general formula:

where R is independently H or a C₁ to C₁₀ hydrocarbon and i is from 1 to5.
 161. The method of claim 160, wherein the C₂-C₁₀ α-olefins areethylene and/or propylene.
 162. The method of claim 135, wherein the CTRcomprises a polymer made with an unsaturated diacid.
 163. The method ofclaim 162, wherein the unsaturated diacid is selected from the groupconsisting of maleic acid, itaconic acid, citraconic acid, and2-pentenedioic acid.
 164. The method of claim 135, wherein the CTRcomprises a polymer made with an anhydride of an unsaturated diacid.165. The method of claim 164, the anhydride is selected from the groupconsisting of maleic anhydride, itaconic anhydride, citraconicanhydride, and 2-pentendioic anhydride.
 166. The method of claim 135,wherein the CTR comprises a polymer made with a monoester of anunsaturated diacid.
 167. The method of claim 166, wherein the monoesteris selected from the group consisting of a monoester of maleic acid, amonoester of itaconic acid, a monoester of citraconic acid, and amonoester of 2-pentenedioic acid.
 168. The method of claim 135, whereinthe CTR is selected from the group consisting of an amine-containingpolymer, an epoxy-containing polymer, a polar copolymer, a polymer madefrom an unsaturated diacid, a polymer made from a monoester of anunsaturated diacid, a polymer made from an anhydride of an unsaturateddiacid, and a polyolefin grafted with(meth)acrylic acid.
 169. The methodof claim 135, wherein the CTR is selected from the group consisting ofan amine-containing polymer, an epoxy-containing polymer, an esterpolymer, a vinyl ester polymer, a polymer made from an unsaturateddiacid, a polymer made from a monoester of an unsaturated diacid, apolymer made from an anhydride of an unsaturated diacid, and apolyolefin grafted with(meth)acrylic acid.
 170. A composite articleformed by the method comprising: (a) providing a laminate comprising anionomer layer and a tie-layer comprising a (co)extrudable tie resin(CTR); (b) forming a shape from the laminate, resulting in a shapedlaminate; and (c) securing a substrate material to the shaped laminate.171. The composite article of claim 170, wherein the laminate isthermoformed.
 172. The composite article of claim 170, wherein the CTRcomprises a copolymer of one or more C₂-C₁₀ α-olefins and one or moreethylenically copolymerizable amine-containing monomers, the copolymerhaving amine groups that may be represented by the general formula:

where each R is independently H or a C₁ to C₁₀ hydrocarbon and R′ is abond or a C₁ to C ₁₀ hydrocarbon.
 173. The composite article of claim172, wherein R is H and R′ is a bond.
 174. The composite article ofclaim 172, wherein the C₂-C₁₀ α-olefins are ethylene and/or propylene.175. The composite article of claim 170, wherein the CTR comprises anepoxy-containing polymer comprising a copolymer of C₂-C₁₀ α-olefins andepoxy-containing monomers.
 176. The composite article of claim 175,wherein the epoxy-containing monomer is represented by the generalformula:

where each R is independently H or a C₁ to C₁₀ hydrocarbon and R′ isindependently a bond or a C₁ to C₁₀ hydrocarbon.
 177. The compositearticle of claim 175, wherein the C₂-C₁₀ α-olefins are ethylene and/orpropylene.
 178. The composite article of claim 175, wherein theepoxy-containing monomers are selected from the group consisting ofglycidyl acrylate and glycidyl methacrylate.
 179. The composite articleof claim 175, wherein the copolymer further comprises an ester monomerrepresented by the general formula:

where each R is independently H or a C₁ to C₁₀ hydrocarbon; each R′ isindependently a bond or a C₁ to C₁₀ hydrocarbon; and R″ is a C₁ to C₁₀hydrocarbon.
 180. The composite article of claim 179, wherein the estermonomer is selected from the group consisting of methyl(meth)acrylate,ethyl(meth)acrylate, propyl(meth)acrylate, and butyl(meth)acrylate. 181.The composite article of claim 170, wherein the CTR comprises a grafted,epoxy-containing polymer represented by the general formula:


182. The composite article of claim 170, wherein the CTR comprises agrafted, epoxy-containing polymer produced by grafting epoxy-containingmonomers onto C₂-C₁₀ α-olefins polymers.
 183. The composite article ofclaim 182, where the C₂-C₁₀ α-olefins polymers are ethylene and/orpropylene polymers.
 184. The composite article of claim 170, wherein theCTR comprises an epoxy-containing polymer, the epoxy-containing polymercomprising glycidyl methacrylate grafted onto polyethylene or acopolymer of ethylene with one or more ester monomers selected from thegroup consisting of methyl(meth)acrylate, ethyl(meth)acrylate,propyl(meth)acrylate and butyl(meth)acrylate.
 185. The composite articleof claim 170, wherein the CTR comprises an acidic copolymer.
 186. Thecomposite article of claim 185, wherein the acidic copolymer is abipolymer of C₂-C₁₀ α-olefins and acidic monomers represented by thegeneral formula:

where R is H or a C₁ to C₁₀ hydrocarbon and R′ is a bond or a C₁ to C₁₀hydrocarbon.
 187. The composite article of claim 186, where the C₂-C₁₀α-olefins are ethylene and/or propylene.
 188. The composite article ofclaim 185, wherein the acidic copolymer is a bipolymer of ethyleneand/or propylene and acrylic acid and/or methacrylic acid.
 189. Thecomposite article of claim 170, where the CTR comprises a bipolymer ofC₂-C₁₀ α-olefins and ethylenically copolymerizable ester monomers,represented by the general formula:

where R is H or a C₁ to C₁₀ hydrocarbon; R′ is a bond or a C₁ to C₁₀hydrocarbon; and R″ is a C₁ to C₁₀ hydrocarbon.
 190. The compositearticle of claim 189, where the C₂-C₁₀ α-olefins are ethylene and/orpropylene.
 191. The composite article of claim 189, wherein the estermonomer is selected from the group consisting of methyl(meth)acrylate,ethyl(meth)acrylate, propyl(meth)acrylate, and butyl(meth)acrylate. 192.The composite article of claim 170, wherein the CTR comprises acopolymer of C₂-C₁₀ α-olefins and vinyl ester monomers represented bythe formula:

where each R is independently H or a C₁ to C₁₀ hydrocarbon.
 193. Thecomposite article of claim 192, wherein the C₂-C₁₀ α-olefins areethylene and/or propylene.
 194. The composite article of claim 192,wherein the copolymer further comprises another ester monomer, theanother ester monomer represented by the general formula:

where each R is independently H or a C₁ to C₁₀ hydrocarbon; each R′ isindependently a bond or a C₁ to C₁₀ hydrocarbon; and R″ is a C₁ to C₁₀hydrocarbon.
 195. The composite article of claim 170, wherein the CTRcomprises a copolymer of ethylene and/or propylene and vinyl acetate,optionally copolymerized with butyl(meth)acrylate.
 196. The compositearticle of claim 170, wherein the CTR comprises grafted polymers ofC₂-C₁₀ α-olefins, ethylene vinyl ester copolymers (based on from C₁ toC₁₀ acids), ethylene(meth)acrylate ester copolymers (made from C₁ to C₁₀alcohols) and a (meth)acrylic acid group, the (meth)acrylic acid grouprepresented by the general formula:

where R is independently H or a C₁ to C₁₀ hydrocarbon and i is from 1 to5.
 197. The composite article of claim 198, wherein the C₂-C₁₀ α-olefinsare ethylene and/or propylene.
 198. The composite article of claim 170,wherein the CTR comprises a polymer made with an unsaturated diacid.199. The composite article of claim 198, wherein the unsaturated diacidis selected from the group consisting of maleic acid, itaconic acid,citraconic acid, and 2-pentenedioic acid.
 200. The composite article ofclaim 170, wherein the CTR comprises a polymer made with an anhydride ofan unsaturated diacid.
 201. The composite article of claim 200, theanhydride is selected from the group consisting of maleic anhydride,itaconic anhydride, citraconic anhydride, and 2-pentendioic anhydride.202. The composite article of claim 170, wherein the CTR comprises apolymer made with a monoester of an unsaturated diacid.
 203. Thecomposite article of claim 202, wherein the monoester is selected fromthe group consisting of a monoester of maleic acid, a monoester ofitaconic acid, a monoester of citraconic acid, and a monoester of2-pentenedioic acid.
 204. The composite article of claim 170, whereinthe CTR is selected from the group consisting of an amine-containingpolymer, an epoxy-containing polymer, a polar copolymer, a polymer madefrom an unsaturated diacid, a polymer made from a monoester of anunsaturated diacid, a polymer made from an anhydride of an unsaturateddiacid, and a polyolefin grafted with(meth)acrylic acid.
 205. Thecomposite article of claim 170, wherein the CTR is selected from thegroup consisting of an amine-containing polymer, an epoxy-containingpolymer, an ester polymer, a vinyl ester polymer, a polymer made from anunsaturated diacid, a polymer made from a monoester of an unsaturateddiacid, a polymer made from an anhydride of an unsaturated diacid, and apolyolefin grafted with (meth)acrylic acid.
 206. The composite articleof claim 170, wherein the CTR comprises a copolymer of one or more C₂ toC₁₀ α-olefins and carbon monoxide.
 207. The composite article of claim206, wherein the copolymer is further copolymerized with one or moreethylenically copolymerizable acidic monomers represented by the generalformula:

wherein R is H or a C₁ to C₁₀ hydrocarbon; R′ is a C₁ to C₁₀hydrocarbon; and n is 0 or
 1. 208. The composite article of claim 206,wherein the copolymer is copolymerized with one or more ester monomersrepresented by the general formula:

wherein R is H or a C₁ to C₁₀ hydrocarbon; R′ is a C₁ to C₁₀hydrocarbon; R″ is a C₁ to C₁₀ hydrocarbon; and n is 0 or 1; or

wherein each R is independently H or a C₁ to C₁₀ hydrocarbon.